Bodying drying oils with cellulose



. Patented Aug. 12, 1941 UNITED] STATES PATENT OFFICE 1 I 2,252,527 3 BODYING nnrmgfigggvrrn Joseph L. Sheri: and Norman R'. Peterson, Midland, Mich, assignors to The Dow Chemical Company, Midland, Mich, a corporation of- Michigan No Drawing.

Application June 3, 1938,

Serial No. 211,600

12 Claims.

This invention relates .to the art of 'bodying drylngoils and especially to a method whereby such oils may be bodied in a short time and with .the production of a more'satisfactory product than is obtained in the customary long time heat- 5 4 bodying processes;

It is well known that drying oils may be cooked I at elevated temperatures to produce an oil which has desirable properties not possessed by the raw oil. The cooking process is referred to as a bodying process since the product obtained therewith has greater viscosity than does the raw oil. A bodied varnish voil has good flow char-' acteristics, readily wets pigments, and deposits films which ultimately .dry with a high gloss and 16 of a much greater resistance to water than do the films deposited from a raw oil. The varnish oils bodied by the old and well-known cook- 'ing processes are not in all respects satisfactory since they have an increased acidity as compared with the raw oil,- tend to sag when formulated into enamels and other coating compositions, are relatively tacky when spread as a film while in the liquid state, form films which are not appreciably tougher than those obtainable from the 20 raw oil compositions, and may dry more'slowly than the raw oil. The bodying operation itself, as ordinarily carried out, requires long periods of time, i. ,e., from 5 or 6 hours to as much as 2 or 3 days, the duration of thecooking operation depending in part upon the type of oil, the viscosity desired, and the temperature used.

Various attempts have been made to incorporate cellulose ethers in varnish oil compositions, generally with little success. The cellulose ethers are not soluble in varnish oils at ordinary temperatures norare they readily incorporated in drying oils at elevated temperatures under the conditions heretofore reported. It has been observed that when cellulose ethers are added to drying oils and heated to the temperatures at which such oils .are ordinarily cooked in bodying operations, the resulting product when cooled to room temperature is a non-flowable gel. llhe gel itself is frequently non-uniform and is'immiscible with or insoluble in the customary var nish thinners such as naphtha and the like. Such products have been found useful, for example, as pore fillers and the like, but their insolubility in varnish vehicles and their inability to flow makes them useless as varnish components. a

It is an object of the present invention to provlde a cellulose ether-varnish oil composition which is miscible with or soluble in varnish vehiclessuch. as naphtha and'which may be prethe range between pared in a relatively short period of time as compared with the time required for the bodying of varnish oils by cooking methods alone. It is a further object to provide such a composition which is flowable at room temperature. It is another object of. the invention to provide a cellulose ether-drying oil composition characterized by being relatively free from tack in the liquid state when spread as a film, by having good.

pigment wetting properties, being low in acidity, showing little-tendencyto sag, drying at an accelerated rate as compared with ordinary heatbodied oils, being miscible with varnish thinners,

and forming films which are appreciably tougher than those obtained from raw or heat-bodied oils.

We have found that the foregoing objects may" be attained by cooking a relatively small amount, e. g., ordinarily from 1. to 15 per cent, of ethyl cellulose with a drygiog oil at a temperature in a ut 500 and about 600 F. Cooking is continued while the composition forms the gelatinous type; of product previously inentioned, and is carried on through this stage unt ll a product is obtained which is flowable at room temperature..- The so-formed material may be described as a sol rather than a gel. ,The s0- 7 formed sols are all miscible with equal weights of V. M. & 'P. naphtha. The gels formed in the early cooking stages are insoluble in such naphtha, but during the later stages of the cooking or bodying operation, while the composition is in a state of transition from the'gel to the sol form, products are obtained which will tolerate an equal weight .of naphtha and similar varnish thinners, and will form a clear solution even though these thinners are non-solvents for cellulose ethers alone,

In carrying out our invention, from 1 15 per cent (more may be employed t6 produce a product of greater viscosity) of ethyl cellulose. having an ethoxyl contentbetween 42 and per cent, is stirred into drying oil such as linseed oil, soybean oil, perilla oil, or menhaden colored final product than is obtained lf-the oil and ethyl cellulose are mixed at room temperature and then heated to effect solvation r the ethyl cellulose in oil. If the apparatus in which the cooking is to be carried out is, heated in inert anda light colored product willbe obtained; event the time required to produce a cellulose After the ethyl cellulose has been added to the ether-bodied'drying oil is only a fraction of the oil, the cooking temperature is raised to and time required for heat-bodying such oils. To 'held between 500 and 600 F. Samples taken illustrate, it 3 per cent oi ethyl cellulose is added from the cook immediately after addition of the to a varnish grade of linseed oil while the latter ethyl cellulose are, when cooled, Y hon-uniform, is being heated, at about-100 F., it will require ,lumpy" liquids or extremely cloudy gels, deapproximately 80 minutes at 520 F. or only 25 pending in part on the amount of ethyl cellulose minutes at 560 F. to produce the completely present and in part on the temperature oi the soluble,'flowable, cellulose ether-bodied oil.

cook. At this stage no appreciable reaction has The viscosity of oils bodied by the present taken place between the oil andthe ethyl cellu l5 process varies according to the per cent and type lose and the componentsoi the mixture are not of ethyl cellulose employed, the cooking schedule, mutually compatible. I and the acid number of the original oil. High As cooking proceeds, samples taken periodically percentages of ethyl cellulose produce high from the cook become increasingly clear, proviscosity oils. Similarly, ethyl cellulose 01 high ducing at one stage in the operation, which ap- 20' intrinsic solution viscosity produces higher viscospears to existfor a considerable period of time, ity oils than low viscosity type ethyl celclear solutions which when cooled form clear, lulose. Prolonged heating oi the ethyl celsubstantially immobile gels. Continued cooking lulose-oil composition, either before or alter-re results 'in the formation of clearer less rigid action has occurred between the oil and the gels, succeeded by the formation of a composig5 ethyl cellulose, tends to reduce the viscosity tion which is partially gel and partially sol, and of the cellulose ether-bodied oil. The lower the finally by a clear, flowable sol. Samples taken acid number of the original oil, the longer will I from the cook Just prior to conversion of the be the cooking time required and the higher will composition to flowable sols, and throughout the be'the resultant viscosity. We preier, however, sol stage, all form clear solutions with equal 80 to employ thosejdrying oils which have an acid weights of V. M. 81 P. naphtha. Such naphtha number in the range which has been found satissolutions, it spread upon a surface, will deposit factory for preparatiomoi varnishes from heatclear, tough films. 1 bodied oil, namely, between0.2 and 5.0 per cent. I While the oil and ethyl cellulose are compatible v Exam 2 1 throughout the clear gel stage. the ethyl cellulose 85 The following table-sets forth the conditions has not become entirely oil-soluble. The third 1 i employed in a number of our experimental runs, or final stage in the process which is character- I in each 0! which a flowable ethyl cellulose-bodied ized by the entire disappearance of the visible drymg on was produced In the said table mm gel structure and which" we have previously re I l to 3, inclusive, are a study of the effect of varyi'erred to as the sol stage, yields a material which 40 I 1 ing percentages of ethyl cellulose, runs 3 and l is not only clear and flowable, but which is as illustrate the effect on the time required or vary homogeneous as any heat-bodied varnish oil and ing the temperature to which the composition is is more viscous than the same oil subjected to I the same cooking schedule but without the celheated runs mcluswe are a study of the luiose ether applicability of the process to various types of drying oils; runs 8-12, inclusive, illustrate the efgfig g gigg m illustrate the practice fect of varying acid numbers in the original oil g I A .MPLE 1 .upon the viscosity oi the bodied oil produced; 1 Y 1 runs 13 and 14 compare the eil'ect upon the final Table I is a detailed study of a typical soy 50 oil viscosity of the initial intrinsic solution vis- I been oil-5 per cent ethyl cellulose cook, showing cosity of the ethyl 'cellulose;' and runs 15-17, the various stages through which the 'composiinclusive, which were made in an atmosphere oi tion passes during the bodying operation. carbon dioxide, are a series illustrating the eflect Table- I 1 f A m Viscosi in Viscosityln Tim e seams. mess; minutes F removed fs; gg composition at ,insolvent' at F. 11 F.

I 0 s0 p 0.05

310 1 0.1 27 400 Ethyl cellulose added 111 500 a 0.2 0.5 42 s40 a 0.00 0.54 41 1 510 4 1.10 1.8 62 510 a 1.34 as s1 s10 0 1.42 2.0 e2 510 a 1 1.44 1.9 a1 1110 a 1.55 as 1.8 12 570 0 1.02 31 11 use 10 1.12 22 1 a s2 sac- 11 1.14 18 1 a s1 1 s00 12 1.14 18 1 a 02 415 1a 1.11 18 1 a 01 I I 460 14 1.11 1a atmosphere, e. g., carbon dioxide or nitrogen the ethyl cellulose may be added to the oil at any temperature from room temperature to the final top heat encountered in the cooking operation,

The time required to eflect the transition from the incompatible stage through the uniform stifl gel stage to the sol varies inverselyas the temperature employed during the cooking. In any Viscosity in solvent determined on a solution consisting of 76% by weight of the oil-ethyl cellulose compohsse .Inconfpatibilltyno reaction-cloudy g Phase II.--Clear ge1'reactlon proceeding mdparts oi butsnol, by volume.

rum TIL-Clear viscoussol or mm mixture, miscible with on equal weight-oi naphtha.

of prolonged heating of th'ecomposition at "top heat" during the cooking operation. Theoriginal ethyl cellulose viscosity is determined at- 77' I". on a 5 per cent solution thereof by weight in a mixture of 80 parts of toluene and 20 parts of ethanol, by volume.

J employed in the formulation of varnishes, paints, and similar air-drying coating compositions. As shown by Examples .3 and 4,.tung oil may he used when properly treated to retard gelation of the oil. In general, then, the oils which may be used are those which are not subject to quick Table II Original oll Ethyl cellulose Cooking schedule Resultant oil I Time at Cooling Run Time to Temp of Top top heat Total time time, 1 Acid Kind acid N Percent Vise. top heat, EthoceP' heat to break at top heat, top heat Visor N0 1 minutes addition gel, utes to 400 F.,

\ minutes 1 minutes 2.2 3 93 40 450 30 41 3. 9 2.9 2. 2 5 93 58 .70 35 8 3. 4 2. 2 18 93 40 450 30 41' 44 3. l 2. 2 v 8 93 38 450 100 85 2. 7 1. 5 7 87 45 400 15 38 40 2.0 1.5 7 87 '41' 400 15 k 38 40 2.2 l. 9 7 87 42 400 15 38 40 2.7 0.5 44 31 0.5 0.94 0. 5 5 87 42 400 30 31 18 1.6 0.7 5 87 45 400 80 30 17 1.7 0. 9 5 87 .400 30 l 33 13 1.8 1. 1 5 87 42 400 30 iii 12 1. 9 1. 1 10 K 87 400 30 30 105 2.2 1. 5 10 10 82 470 30 55 23 2. 0 0. 5 5 98 86 450 8 60 40 1. 3 0. 5 5 98 88 .450 13 60 26 1. 4 0.5 5 98 90 450 30 60 20 I 1. 8

Gel broken on down heat."

v EXAMPLE 3 To 85 parts by weight of tung oil was added. 5 parts of glycerine, to retard gelation of the oil, and 10 parts by weight of a 20 centipoise ethyl cellulose having an ethoxyl content of about 48.5 per cent.- stirred together at room temperature and the mixture heated to500 F. over a period of 26 minutes, when a cooled sample removed from the cook remained clear. The batch wasallowed to cool, and was found" to be a clear, uniform, fiowabl'e, viscous oil. The product was completely miscible with an equal weight of mineral spirits.

. ExAmLn 4 A com-position cellulose was similar in properties to a linseed The various ingredients were prepared from .a mixture of equal volumes of tung and linseed oils and ethyl gelation when heated to 500 to 600 F. ,Such

oils may be'those which are naturally free from quick gelation on heating to such temperatures; or th'ey'may be oils, such as tung oil, which are treated to retard gelation. The oil employedv may be either a raw oil, refined oil, or an oil which has already beenbodied by heat.

The herein-described process is useful in the preparation of bodied oils which may be employed alone, as inthe preparation of oil-finished surfaces, or in combination with raw oil's, resins, gums, wood stains, pigments, and the like, in any of the types of coating compositions in which heat-bodied 'oils are customarily employed. The increased viscosity of the composioil-ethyl cellulose composition prepared in like lose ethers may be employed in a similar manner to produce analogous oil compositions. For example, we have employed methyl ethyl cellulose and have found it to be as'satisfactory in many respects as the ethyl cellulose-oil composition.

In a like manner, other cellulose alkyl others such as ethyl propyl cellulose, butyl cellulose, ethyl butyl cellulose, and the like, may be employed.

examples herein are linseed, soy bean, perilla, oiticica, and tung oils. There maybe used instead sunfiower oil, safilower oil, menhaden oil, and other drying or polymerizing oils ordinarily paints, etc.

tion and toughness of the films deposited thereby as compared with those producible from heatbodied oils alone make our compositions ex,- tremely useful in the preparation of varnishes,

Other modes of applying the principle of our invention may be employed instead of the one 'explained, change being made as regards the process herein disclosed, provided the step or steps stated by any of the following claims or the equivalent of such stated step or steps be employed, or the products recited in the. claims I be thereby obtained.

We therefore particularlypolnt out and distinctly claim as our-invention: V

1.- The process which consists in (l) mixing from 1 to about 15 per cent-of a cellulose alkyl ether with correspondingly from 99 to about 85 per cent of a drying oil selected from the group consisting of linseed oil, menhaden' oil, oiticica a 70. The oils which have been shown in the various oil, perilla oil, s'ailiower oil, soybean oil, sunflower oil, tung oil treated to retard gelation,and mixtures thereof, (2) heating. the oil-cellulose ether mixture to a temperature in the range from 500 to 600 F., (3) cooking the mixture in the said temperature rangela) to produce a non-uniform. gel, cooled samples of which are v immiscible with mineral spirits, (bl continuing the cooking at 500 to 600 F. through an intermediate physical stage of the oil-cellulose ether mixture wherein cooled samples are apparently uniform and less rigid gels than those in the first stage, and (c) continuing the cooking at 500 to 600 F. to produce a third and final stage of the oil-cellulose ether mixture, whereof cooled samples are clear and flowable, and are miscible with equal weights of mineral spirits to form clear solutions, the product being as homogeneous as, and more viscous than the same drying oil subjected to the same cooking schedule but without the cellulose ether.

2. The process which consists in (1) mixing from 1 to about 15 per cent of a cellulose alkyl ether with correspondingly from 99 to about 85 per cent of a drying oil selected from the groupconsisting'of linseed oil, menhaden oil, oiticica oil, perilla oil,' saillower oil, soybean oil, sunower oil, tung on treated to retard gelation, and mixtures thereof, (2) heating the oil-cellulose ether mixture to a temperature in the range from 500 to 600 F., (3) cooking the mixture in the said temperature range (a) to produce a non-uniform gel, cooled samples of which are immiscible with mineral spirits, (b) continuing the cooking at 500 to 600 F. through an intermediate physical 'stage of the oil-cellulose ether mixture wherein cooled samples are apparently uniform and less rigid gels than those in the first stage, and (c) continuing the cooking at 500 to 600 F. to produce a third and final stage of the oil-cellulose ether mixture, whereof cooled samples are clear and flowable, and are miscible with equal weights of mineral spirits to form treated to retard gelation, and mixtures thereof,

- while the said oil is being heated at a temperature of from 300 to 500 F (2) heating the oil-cellulose ether mixture to a temperature in the range from 500' to 600- F., (3) cooking the mixture in the said temperature range (a) to produce a non-uniform gel, cooled samples of which are immiscible with mineral spirits, (b) continuing the cooking at 500 to 600 F. through an intermediate physical stageof the oil-cellulose ether mixture wherein cooled samples are apparently uniform and less rigid gels than those in the first stage, and (c) continuing the cooking at 500 to 600 F. to produces. thirdland flnal stage of the oil-cellulose ether mixture, whereof cooled samples are clear and flowable, and are miscible with equal weights of mineral spirits to form clear'solutions, then (4) discontinuing the cooking operation, and (5) cooling the product which is as homogeneous as, and more viscous than the same drying oil subjected-to the same cooking schedule but without the celluloseether.

5. The process as claimed in claim 3, wherein the drying oil employed is linseed oil.

been treated to retard gelation.

clear solutions, then (4) discontinuing the cooking operation, and (5) cooling the product which is as homogeneous as, and more viscous than the same drying oil subjected to the same cooking schedule but without the cellulose eth r.

3. The process which consists in- (1) mixing from 1 to about 15 per cent of ethyl cellulose with correspondingly from 99 to about 85 percent of.

a'drying oil selected from the 'group consisting oi linseed oil, menhaden oil, oiticica oil, perilla oil, saiiiower oil,-soybean oil, sunflower oil, tung oil treated to retard gelation, and mixtures thereof, (2) heating the oil-cellulose ether mixture'to' a temperature in the range from 500 to 600 F., (3) cooking the mixture in the said temperature range (a) to produce a non-uniform gel, cooled samples of which are immiscible with mineral spirits, (b) continuing the cooking at 500 to 600 F. through an intermediate physical stage of the oil-cellulose ether mixture wherein cooled samples are apparently. uniform and less rigid gels than those in the first stage, and (c) continuing the cooking at 500 to 600 F. to produce a third and final stage of the oil-cellulose ether mixture, whereof cooled samples are clear and flowable, and are miscible with equal weights of mineral spirits to form clear solutions, then (4) discontinuing the cooking) operation, and (5) cooling the product which is as homogeneous as, and more viscous-than the same drying oil subjected to the same cooking schedule but without the cellulose ether. M

4. The process which consists in (1) mixing from 1 to about 15per cent of ethyl cellulose-with correspondingly from 99 to about 85 per cent of a drying on selected from the group consisting of linseed oil, menliaden oil, oiticica oil, perilla oil, safliower oil, soybean oil, sunflower oil, tung oil '8. A clear, flowable cellulose alkyl-ether-bodied oil selected from the group consisting of linseed oil, menhaden oil, oiticica oil, perilla oil, safllower oil, soybean oil, sunflower oil, tung. oil, treated to retard gelation. and mixtures thereof being identical with the product obtained by the method of claim 2, and containing froni 1 to 15 per cent of the cellulose ether, and correspondingly from 99 to per cent of the oil.

- 9.-A clear, flowable ethyl cellulose-bodied oil selected from-the g oup consisting of linseed oil, ,menhaden oil, oitici a oil, perilla' oil, saiilower oil, soybean oil, sunflower oil, tung oil treated to retard gelation, and mixtures thereof, being identical with the product obtained by the method of claim 3, and containing from 1 to 15 per cent from 99 to 85 per cent of the oil.

10. A clear, flowable ethyl cellulose-bodied linseed oil, being identical with the product ob tained by the methodof claim 3 when the oil employed is linseed oil, and containing from 1 to 15 per cent of ethyl cellulose and correspondingly from 99 to 85 per cent of the oil.

11. A clear, flowable ethyl cellulose-bodied soybean oil, being identical with the product obtained by the method of claim 3 when the oil employed is soybean oil, and containing 1 to 15 per cent of ethyl cellulose and correspondingly from 99 to 85 per cent of the oil.

12. A clear, flowable ethyl cellulose-bodied tung 011, being identical with the product obtained by the method of claim 3 when the oil employed is tung oil which has been treated to retard gelation, and containing from 1 to 15 per cent of ethyl cellulose and correspondingly from 99 to 85 per cent of the oil.

JOSEPH L, SHERK. NORMAN PETERSON.

6'. The process as. claimed in claim 3, wherein 

